Imidyl compounds

ABSTRACT

The imidyl compounds, according to the invention, of the formula I are suitable for the manufacture of polymers which can be crosslinked by light, which polymers can be, for example, polyesters, polyamides, polyamide-imides, polyimides, polyester-polyamides, polyester-amide-imides, polyethers, polyamines, polysaccharides and polysiloxanes. Polymers of this type are suitable for carrying out photochemical processes. Compared with known polymers, the polymers based on the imidyl compounds according to the invention have the advantage that they are photochemically substantially more sensitive. In addition, this sensitivity can also be further increased effectively by a combination with sensitizers.

This is a divisional of application, Ser. No. 696,346, filed on June 15,1976, now U.S. Pat. No. 4,107,174, issued on Aug. 15, 1978.

The present invention relates to new imidyl compounds and processes fortheir manufacture.

The new imidyl compounds correspond to the formula I ##STR1## wherein ndenotes the number 1 or 2, R₁ and R₁ ' independently of one anotherdenote alkyl with 1-4 carbon atoms or R₁ and R₁ conjointly denote a tri-or tetra-methylene grouping which is optionally substituted by a methylgroup and Y denotes an alkylene group with 1-20 carbon atoms, whichoptionally contains hetero-atoms, a cycloalkylene group with 5 or 6carbon atoms, an arylene group with 6 to 10 carbon atoms, a ##STR2##group, in which Q represents a direct bond, --NH--, --O--, --CH₂ --,##STR3## group with 7 or 8 carbon atoms, and when n=1, X denotes a groupof the formulae and, when n=2, X denotes halogen, --COOH, --COO⁻ M⁺,--COO-alkyl, --CN, --CO--O--alkenyl, --O--alkenyl, --O--CO--alkenyl,--NH-alkyl, --NH--alkenyl, --NH--CC--alkenyl, --SH, --S--alkenyl or##STR4## and, when Y represents a cycloalkylene, arylene, aralkylene oralkylarlyene group, or a ##STR5## group, according to the definition, Xalso denotes --OH or --NH₂, and R₂ and R₃ independently of one anotherdenote --OH or --NH₂, the two R₄ 's each denote --OH, --Cl, alkoxy with1-12 carbon atoms, substituted or unsubstituted phenoxy or --O⁻ M⁺ orone R₄ denotes --OH and the other R₄ denotes ##STR6## and R₅ denotes--OH, --Cl, alkoxy with 1-12 carbon atoms, unsubstituted or substitutedphenoxy or a --O⁻ M⁺ group, the two R₆ 's have the same meaning as R₄ orthe two R₆ 's conjointly represent --O--, R₇ and R₈ independently of oneanother denote hydrogen, --OH, --Cl, --O-alkyl, --O-phenyl, --OCO-alkyl,--OCO-phenyl, --NH-alkyl or ##STR7## R₉ represents --CH═CH₂, --CH₃,phenyl or the group --O--Si--CH₃)₃ or R₉ has the same meaning as R₇ orR₈, or R₇ and R₈ conjointly form the group ##STR8## M⁺ denotes an alkalimetal cation or a trialkylammonium cation with 3-24 carbon atoms, Zdenotes a straight-chain or branched alkylene group with 1-12 carbonatoms, especially the --CH₂ --group, Q₁ and Q₂ independently of oneanother denote hydrogen or methyl, m denotes the number 2, 3 or 4 and qdenotes the number 2 or 3 and in the above groups alkyl parts contain1-8 carbon atoms and alkylene parts contain 2-4 carbon atoms.

Compounds, according to the invention, of the formula Ia ##STR9##wherein n, R₁, R₁ ' and Y have the meaning indicated under formula Iand, when n=1, X' represents a group of the formulae ##STR10## and, whenn=2, X' has the same meaning as X and what has been stated under formulaI applies in respect of R₂ to R₉, Q, Q₁, M⁺, m, q, alkyl parts andalkylene parts, can be obtained when an amine of the formula II

    H.sub.2 N--(Y).sub.n-1 X.sub.1                             (II)

wherein what has been stated under formula I applies in respect of Y andn and, when n=1, X₁ represents a group of the formulae ##STR11## and,when n=2, X₁ represents a group corresponding to X' and the two R₄ ''sor the two R₆ ''s each denote --OH, alkoxy with 1-12 carbon atoms,unsubstituted or substituted phenoxy or --O⁻ M⁺, or one R₄ ' or one R₆ 'denotes --OH and the other R₄ ' or other R₆ ' denotes a group ##STR12##and R₅ ' denotes --OH, alkoxy with 1-12 carbon atoms, unsubstituted orsubstituted phenoxy or --O⁻ M⁺ and what has been stated under formula Iapplies in respect of alkenyl groups, R₁, R₁ ', R₂, R₃, R₇, R₈, R₉, Q₁,M⁺, m and q, is reacted, in at least the stoichiometric amount, with ananhydride of the formula III ##STR13## wherein R₁ and R₁ ' have themeaning indicated under formula I, and the resulting compounds areoptionally converted into derivatives, according to the definition, ofthe formula Ia.

According to a modified procedure, compounds, according to theinvention, of the formula Ib ##STR14## can be manufactured when acompound of the formula IIIa ##STR15## is reacted, in at least thestoichiometric amount, with a halide of the formula IV ##STR16##

In the above formulae Ib, IIIa and IV, R₁, R₁ ', Z, Q₁ and Q₂ have themeaning indicated under formula I: M₁ represents an alkali metal,especially sodium or potassium, and Hal denotes bromine and, above all,chlorine.

According to the process of the invention--in contrast to analogousreactions with maleic anhydride and phthalic anhydride--the anhydridesof the formula III can be reacted direct with the compounds of theformula II, that is to say without additional measures, such astreatment with agents which eliminate water, to give imidyl derivativesof the formula Ia.

Moreover, the imidyl derivatives of the formula I are obtained, by theprocess according to the invention, in good to very good yields and aredistinguished by a high stability towards acids and bases.

Alkylene, cycloalkylene, arylene, aralkylene, alkylarylene or bicyclic,non-condensed, carbocyclic-aromatic groups according to the definition,which are represented by Y, can be unsubstituted or substituted by, forexample, alkyl and alkoxy groups with 1-4 carbon atoms, nitro groups orhalogen atoms, such as chlorine, bromine or fluorine.

Alkylene groups Y can be straight-chain or branched and can contain oneor more heter-atoms, especially S or O atoms. Unsubstituted alkylenegroups with 1 to 12 and in particular 2-6 carbon atoms, such as themethylene group, the 1,2- or 1,1-ethylene group, the 1,3- oriso-propylene group, the 2,2-dimethylpropylene group or thehexamethylene, octamethylene or dodecamethylene group, are preferred.

Preferred cycloalkylene groups are unsubstituted cyclopentylene and,above all, unsubstituted cyclohexylene groups.

Examples of suitable arylene groups Y are the 1,2-, 1,3- and1,4-phenylene group, the 1,3-tolylene group, the 3-nitro-1,4-phenylenegroup and the 1,7- and 2,7-naphthylene group. Unsubstituted phenylenegroups are preferred.

Possible aralkylene groups are, in particular, the benzylene group andthe 2-phenylethylene group.

If Y represents a bicyclic, non-condensed, carbocyclic-aromatic group,the latter is, for example, the 2,2'-biphenylylene group or the4,4'-diphenylmethane, 4,4'-diphenylamine or 4,4'-diphenyl ether group.

Particularly preferentially, Y represents an unsubstituted alkylenegroup with 2-6 carbon atoms or the 1,4-cyclohexylene group.

Alkyl or alkoxy groups according to the definition and also alkyl oralkenyl parts of substituents according to the definition can also bestraight-chain or branched.

Examples which may be mentioned of alkyl, alkoxy and alkenyl groupsaccording to the definition are: the methyl, ethyl, propyl, isopropyl,n-butyl, tert.-butyl, n-hexyl, methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, tert.-butoxy, hexyloxy, octoxy, decyloxy, dodecyloxy, vinyl,allyl, methacryl and crotyl group.

R₁ and R₁ ' preferably have the same meaning. Compounds of the formula Iwherein R₁ and R₁ ' each represent the methyl group are veryparticularly preferred.

If X denotes a halogen atom, the latter is bromine or iodine, butespecially chlorine.

If R₄ to R₆ or R₄ ' to R₆ ' represent substituted phenoxy groups, thelatter are, in particular, phenoxy groups which are substituted by nitrogroups, alkyl or alkoxy groups with 1 or 2 carbon atoms, or halogenatoms, such as chlorine or fluorine, such as the 2-, 3- or4-nitrophenoxy group, the 2,4- or 3,5-dinitrophenoxy group, the3,5-dichlorophenoxy group, the pentachlorophenoxy group or the 2-methyl-or 2-methoxy-phenoxy group. Unsubstituted phenoxy groups are preferred.

If n is the number 2, X preferably represents --OH, --COOH, --COO⁻ M⁺,wherein M⁺ =an alkali metal cation, especially Na, --CO--O-alkenyl,--O-alkenyl, --OCO-alkenyl, --NH₂ or --NHCH₃.

When n=1, preferred groups X are: ##STR17## and especially those groupsin which one R₄ or one R₆ denotes --OH and the other denotes ##STR18##or a group ##STR19##

M⁺ represents, for example, the lithium, sodium, potassium,trimethylammonium, triethylammonium or methyldiethylammonium cation orthe tri-n-octylammonium cation. M⁺ preferably represents the sodiumcation.

The compounds of the formulae II, III, IIIa and IV are known or can bemanufactured in a manner which is in itself known.

Amines of the formula H₂ N--Y--O-alkenyl, N₂ N--Y--S-alkenyl and H₂N--Y--NH-alkenyl or H₂ N--Y--NH--CO-alkenyl and H₂ N--Y--O--CO-alkenylcan be obtained, for example, by reacting corresponding aminoalcohols,aminomercaptans or diamines, in the presence of bases, such as K₂ CO₃,triethylamine or pyridine, with alkenyl halides, especially alkenylbromides, or alkenyl acid chlorides respectively.

Amines of the formula H₂ N--Y--CO--O-alkenyl can be manufactured byreacting corresponding aminoacids, or salts thereof, with alkenylhalides, especially alkenyl bromides.

Aminobenzene-dicarboxylic and -tricarboxylic acids and theirderivatives, wherein R₄ ' or R₆ ' represent --OH, --Cl, alkoxy orphenoxy or --O⁻ M⁺, can be employed as such or can be manufactured insitu by reducing the corresponding nitrobenzene-dicarboxylic or-tricarboxylic acids, or derivatives thereof, and used further withoutintermediate isolation.

Amines of this type, wherein X₁ denotes a benzenedicarboxylic or-tricarboxylic acid radical, are preferably used in the form of estersand especially in the form of salts, above all as sodium salts.

Aminobenzene-dicarboxylic and -tricarboxylic acid derivatives, whereinone R₄ ' or, respectively, one R₆ ' represents a group ##STR20## areobtained by reacting the corresponding anhydride with an alkenylalcohol.

The reaction of the amines of the formula II with the anhydrides of theformula III can be carried out in the melt by heating the reactants totemperatures of up to about 250° C., or also in an aqueous,aqueous-organic or organic medium, in which case the reaction is carriedout, depending on the reactants, at temperatures between about 0° C. andthe boiling point.

Appropriately, the anhydride of the formula III is employed in thestoichiometric amount or in a slight recess over the amine of theformula II, for example in an up to about 20% molar excess.

Examples of suitable organic solvents are: optionally halogenatedaliphatic or aromatic hydrocarbons, such as methylene chloride,chloroform, carbon tetrachloride, 1,1,2-trichloroethane,1,2-dichloroethylene, benzene, toluene and chlorobenzene; anhydrousacetic acid; aliphatic and cycloaliphatic ketones, such as acetone,methyl ethyl ketone, cyclopentanone and cyclohexanone; cyclic ethers,such as tetrahydrofurane, tetrahydropyrane and dioxane; cyclic amides,such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone andN-methyl-ε-caprolactam; N,N-dialkylamides of aliphatic monocarboxylicacids with 1-3 carbon atoms in the acid part, such asN,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide andN,N-dimethyl-methoxyacetamide; alkyl esters of aliphatic monocarboxylicacids with a total of 2-6 carbon atoms, such as formic acid methyl,ethyl or n-butyl ester or acetic acid methyl, ethyl or n-butyl ester;hexamethylphosphoric acid triamide (hexametapol);N,N,N',N'-tetramethylurea; tetrahydrothiophene dioxide (sulpholane); anddialkylsulphoxides, such as dimethylsulphoxide and diethylsulphoxide.

Mixtures of solvents of this type can also be employed. Preferredsolvents are dioxane, anhydrous acetic acid, methylene chloride,benzene, toluene, xylene, ethyl acetate, methyl ethyl ketone andchlorobenzene.

The reaction of the alkali metal salts of the formula IIIa with thehalides of the formula IV is also carried out in a manner which is initself known, appropriately in suspension or in a suitable organicsolvent and optionally in the presence of a salt of a quaternary base,such as tetramethylammonium chloride. Polar solvents, such as alcohols,acetone, acetonitrile, N,N-dimethylformamide and dimethylsulphoxide, arepreferred.

The compounds of the formula Ia, which have been manufactured accordingto the invention, can, if desired--and depending on the nature of theamines of the formula II which have been used--be converted in a mannerwhich is in itself known into other compounds, according to thedefinition, of the formula Ia, or into derivatives thereof. Exampleswhich may be mentioned are:

(1) X'=--COCl (derivative) and R₄ and R₆ =--Cl

By reaction of compounds of the formula Ia, wherein X'=--COOH and R₄ toR₆ =--OH or --O⁻ M⁺, or the two R₆ 's conjointly =--O--, with suitablechlorinating agents, such as thionyl chloride, oxalyl chloride andphosgene.

(2) X'=--COOH and R₄ to R₆ =--OH

By hydrolysis of compounds of the formula Ia, wherein X'=--COO⁻ M⁺,--COO-alkyl or --CN, or of compounds of the formula Ia, wherein R₄ andR₆ =--O⁻ M⁺, alkoxy or phenoxy or the two R₆ 's cojointly=--O--, in anacid or alkaline medium, or by alcoholysis of compounds of the formulaIa, wherein X'=--CN, in an acid medium to give the correspondingimino-ether and subsequent hydrolysis of the latter.

(3)=--COO-alkyl and R₄ and R₆ =alkoxy or phenoxy

By reaction of compounds of the formula Ia, wherein X'=--COOH or --COCland R₄ to R₆ =--OH or --Cl, or the two R₆ 's conjointly=--O--, withcorresponding alcohols, or by transesterification of compounds of theformula Ia, wherein X'=--COO-alkyl and R₄ to R₆ =alkoxy or phenoxy.

(4) X'=--NH₂ or --NH-alkyl

By catalytic reduction of compounds of the formula Ia, wherein X'=-CN,and, optionally, subsequent alkylation of the reaction product.

(5) X'=--SH

By treatment of compounds of the formula Ia, wherein X'=halogen, withsuitable sulphur compounds, such as thiourea or Na₂ S.

(6) X'=--O-alkenyl, --NH-alkenyl or --S-alkenyl

By reaction of compounds of the formula Ia, wherein X'=--OH, --NH₂ or--SH, with alkenyl halides, especially bromides, in the presence ofbases, such as K₂ CO₃.

(7) X'=--O--CO-alkenyl

By reaction of compounds of the formula Ia, wherein X'=--OH, withcorresponding unsaturated acids, acid chlorides or esters.

(8) X'=--CO--O-alkenyl

By reaction of compounds of the formula Ia, wherein X'=--COOH (or--COCl), with corresponding unsaturated esters or alcohols in thepresence of acids or bases.

(9) X'=--NH--CO-alkenyl

By reaction of compounds of the formula Ia, wherein X'=--NH₂, withcorresponding acid chlorides. ##STR21##

By reaction of compounds of the formula Ia, wherein the two R₆ 'sconjointly=--O--, with corresponding alcohols. ##STR22##

By reaction of compounds of the formula Ia, wherein n=2, Y=phenylene andX'=--OH, with alkenyl halides and subsequent reaction of the productwith a compound of the formula ##STR23##

Compounds, which are in themselves known, of the formula Ic ##STR24##wherein R₁, R₁ ' and n have the meaning indicated under formula I, Yrepresents an alkylene group which optionally contains hetero-atoms andX" represents --OH or --NH₂, can also be employed for the reactionsaccording to (6), (7) and (9).

Further derivatives of compounds of the formula Ia can be manufacturedas follows:

X'=--CO--O--CHO

By reaction of acid chlorides obtained according to (1) with an alkalimetal salt of formic acid.

X'=--CO--O--CO--CF₃

By reaction of compounds of the formula Ia, wherein X'=--COOH, with CF₃--CO--O--CO--CF₃.

X'=--CO--O--CO--O-alkyl

By reaction of compounds of the formula Ia, wherein X'=--COO⁻ M⁺, withcompounds of the formula Cl--CO--O-alkyl.

X'=--CO--NH--CO-alkenyl

By reaction of acid chlorides with alkenyl acid amides.

X'=--CO--O--(CH₂)₂ --O-alkenyl or --CO--O--(CH₂)₂ --O--CO-alkenyl

By reaction of acid chlorides or esters with corresponding unsaturatedalcohols.

According to another modified process, the amide-carboxylic acids of theformula ##STR25## which are formed as intermediates during the reactionof the amines of the formula II with the anhydrides of the formula III,can be isolated in the form of derivatives, for example as salts, andsubsequently cyclised, chemically or by means of heat, in a known mannerto give compounds of the formula I.

Compounds of the formula I, wherein X represents a group ##STR26## canalso be obtained by reacting a compound, which is in itself known, ofthe formula IIIb ##STR27## with maleic anhydride.

Furthermore, compounds of the formula I wherein, when n=1, X representsa group of the formula ##STR28## can be obtained by reacting ananhydride of the formula IIIc ##STR29## (manufactured by reacting 3- or4-aminophthalic acid with an anhydride of the formula III) with analcohol of the formula ##STR30## or with an aminophenol and subsequentlyfurther converting the resulting reaction product, as indicated under11).

Finally, compounds, according to the invention, of the formula I,wherein X represents a --OH, --NH₂ or --NH-alkyl group, can also beobtained according to another modified process by reacting a compound ofthe formula IIIa ##STR31## wherein R₁ and R₁ ' have the abovementionedmeaning and M₁ represents an alkali metal, especially sodium orpotassium, with a halide of the formula

    Hal--(Y).sub.n-1 X.sub.2

wherein Y and n have the meaning indicated under formula I and X₂denotes --OH, --NH₂ or --NH-alkyl.

When the reaction has ended, the compounds of the formula I are isolatedin a customary manner, for example by filtration or by stripping off thesolvent, and are purified if necessary, for example by washing withwater, recrystallising from suitable solvents, such as methanol,ethanol, benzene or toluene, or by sublimation or distillation.

After the reaction with the anhydride of the formula III, compounds ofthe formula I, wherein X represents a group ##STR32## and the R₆ eachrepresent --OH or --O⁻ M⁺, can, in a manner which is in itself known, becyclised chemcially, that is to say using dehydrating agents, such asacetic anhydride, and/or by the action of heat.

The compounds, according to the invention, of the formula I and theabovementioned derivatives are suitable for the manufacture of polymerswhich are crosslinkable under the influence of electromagnetic waves,especially light, such as polyesters, polyamides, polyamide-imides,polyimides, polyester-polyamides, polyester-amide-imides, polyethers,polyamines, gelatine, polysaccharides and polysiloxanes. Crosslinkablepolymers of this type can be manufactured, for example, by incorporatingcompounds of the formula I into suitably substituted polymers, such aspolyvinyl alcohols, polyanhydrides or polyethers, or by polycondensationwith diamines, diols of aminoalcohols or derivatives thereof andoptionally in the presence of further di-, tri- or tetra-carboxylic acidderivatives.

Crosslinkable polyethers can, for example, also be obtained by apolyaddition reaction of compounds of the formula I with oxides, such asethylene oxide, propylene oxide and styrene oxide, optionally in thepresence of amines, alcohols or phenols.

Finally, crosslinkable polymers can also be obtained byhomopolymerisation of compounds of the formula I or, preferably, bycopolymerisation of such compounds with vinyl comonomers, such as vinylchloride, vinylidene chloride, vinyl acetate, styrene, acrylic acidderivatives and methacrylic acid derivatives or acrylonitrile.

A number of polymers which can be crosslinked under the action of lightare already known. In most of these light-sensitive polymers thephoto-active groups are linked as side-chain substituents to the polymerchain. In this context, the following Japanese Offenlegungsschriftenshould be mentioned in particular: Japanese application 49/128,991,Japanese application 49/128,992, Japanese application 49/128,993,Japanese application 50/5,376, Japanese application 50/5,377, Japaneseapplication 50/5,378, Japanese application 50/5,379 and Japaneseapplication 50/5,380.

In these Japanese patent applications processes for the manufacture oflight-sensitive polymers are claimed and these polymers contain, aslight-sensitive groups, groups of the formula II ##STR33## in which R₈denotes an aromatic radical and R₉ denotes H, halogen, alkyl or --CN.

However, known polymers of this type have the disadvantage that theirphotochemical sensitivity is much too low for special phototechnicalapplications. This characteristic has a negative effect, especially inthat, ultimately, unsharp images or relief images result whencorresponding photomechanical processes are carried out and that theexposure times required are too long.

In the case of these polymers it is also not possible to eliminate thisdisadvantage by using sensitisers for photochemical reactions. That isto say, these known light-sensitive polymers evidently completelyprevent these sensitisers from displaying their action.

The imidyl compounds according to the invention now, surprisingly, leadto polymers which do not display the disadvantages of the knownlight-sensitive polymers. Thus, they display a greater sensitive towardselectromagnetic waves and, in addition, this sensitivity can also befurther increased by a combination with sensitisers.

Crosslinkable polymers of this type are used, for example, as aphotoresist, for the manufacture of photographic materials on the basisof non-silver processes or for the manufacture of printing plates. Theyare distinguished by high sensitivity to light and good quantum yields.

EXAMPLE 1 ##STR34##

126 g (1 mol) of dimethylmaleic anhydride and 115 g (1 mol) of4-aminocyclohexanol are warmed, whilst stirring, to 120°-125° C.(internal temperature) for 30 minutes in an oil bath. After cooling toabout 20° C., the reaction product is dissolved in 500 ml of methylenechloride and the solution is extracted once with 100 ml of 1 N NaOH,whilst cooling with ice. The reaction product is then washed twice withwater and dried over Na₂ SO₄. The solvent is evaporated and the residueis recrystallised from a 1:1 mixture by volume of ethyle acetate andpetroleum ether. 155 g (70% of theory) ofN-(4-hydroxycyclohexyl)-dimethyl-maleimide are obtained; melting point109°-111° C.

Analysis for C₁₂ H₁₇ NO₃ (molecular weight 223.3): calculated C 64.6% H7.7% N 6.3% O 21.5%. found C 64.5% H 7.5% N 6.3% O 21.6%. NMR (CHCl₃):signal for the methyl protons at 1.95 ppm.

Table I which follows indicates further compounds of the formula I whichhave been prepared according to the procedure described in Example 1above, by reacting 2,3-dimethylmaleic anhydride with the amines listed.

                                      Table I                                     __________________________________________________________________________    Examples 2-8                                                                  __________________________________________________________________________                                              Compound                            Ex-                                       of the                              ample                                                                             Compound of           Compound of     formula                             No. the formula I         the formula II  III                                 __________________________________________________________________________         ##STR35##                                                                                           ##STR36##      2,3- dimethyl- maleic anhydride                                               2                                   3                                                                                  ##STR37##                                                                                           ##STR38##      2,3- dimethyl- maleic anhydride                                               4                                   4                                                                                  ##STR39##                                                                                           ##STR40##      2,3- dimethyl- maleic anhydride                                               5                                   5                                                                                  ##STR41##                                                                                           ##STR42##      2,3- dimethyl- maleic anhydride                                               .                                   6                                                                                  ##STR43##                                                                                           ##STR44##      2,3- dimethyl- maleic anhydride     7                                                                                  ##STR45##                                                                                           ##STR46##      2,3- dimethyl- maleic anhydride     8                                                                                  ##STR47##                                                                                           ##STR48##      2,3- dimethyl- maleic anhydride     __________________________________________________________________________                             Tem-                                                                             re-  Melt-                                                        Ex- Reaction                                                                           pera-                                                                            crystal-                                                                           ing Yield                                                                             NMR.sup.(xx)                                         ample                                                                             time ture                                                                             lised                                                                              point                                                                             % of                                                                              (DMSO-d.sub.6)                                       No. minutes                                                                            °C.                                                                       from °C.                                                                        theory                                                                            δ in ppm                       __________________________________________________________________________                    2   60   140                                                                              methanol                                                                           161-                                                                              75  2.0                                                                   162                                                          3   30   150                                                                              ethanol                                                                            206 55  1.9                                                  4   45   180                                                                              methanol                                                                           138-                                                                              50  1.95.sup.(x)                                                          139                                                          5   15   200                                                                              ethanol                                                                            227-                                                                              50  1.95                                                                  230                                                          6   30   200                                                                              ethanol-                                                                           210-                                                                              52  1.95                                                             H.sub.2 O                                                                          212                                                          7   30   250                                                                              tetra-                                                                             232-                                                                              32  2.0                                                              hydro-                                                                             237                                                                      furane/                                                                       H.sub.2 O                                                         8   30   130                                                                              ethyl                                                                              115-                                                                              40  2.0.sup.(x)                                                      acetate                                                                            116                                          __________________________________________________________________________     .sup.(x) (CDCl.sub.3)-                                                        .sup.(xx) Methyl protons of the dimethylmaleimidyl radical               

EXAMPLE 9 ##STR49##

145 g (1.15 mols) of dimethylmaleic anhydride and 150 g (1.15 mols) ofε-amino-caproic acid are dissolved in 700 ml of anhydrous acetic acidand the solution is boiled under reflux for 8 hours. The acetic acid isthen distilled off in a rotary evaporator. The residue is dissolved in500 ml of diethyl ether and the solution is washed once with 100 ml of 1N NaOH, whilst cooling with ice, and twice with water. After drying overNa₂ SO₄ and evaporating the diethyl ether, the residue is crystallisedfrom about 150 ml of isopropyl ether. 209 g (76% of theory) ofN-(caproic acid)-dimethylmaleimide are obtained; melting point 43°-45°C.

Analysis for C₁₂ H₁₇ NO₄ (molecular weight 239.3): calculated C 60.2% H7.2% N 5.9% O 26.8% found C 60.3% H 7.2% N 5.9% O 26.9% NMR (CHCl₃):signal for the methyl protons at 2.0 ppm.

Table II which follows indicates further compounds of the formula Iwhich were prepared according to the procedure described in Example 9above, by reacting 2,3-dimethylmaleic anhydride with the amines listed.

                                      Table II                                    __________________________________________________________________________    Examples 10-16                                                                __________________________________________________________________________                                         Compound                                                                      of the                                   Ex.                                                                              Compound of         Compound of   formula                                  No.                                                                              the formula I       the formula II                                                                              III                                      __________________________________________________________________________    10                                                                                ##STR50##          H.sub.2 N(CH.sub.2).sub.2 COOH                                                              2,3- dimethyl- maleic anhydride          11                                                                                ##STR51##                                                                                         ##STR52##    2,3- dimethyl- maleic anhydride          12                                                                                ##STR53##                                                                                         ##STR54##    2,3- dimethyl- maleic anhydride          13                                                                                ##STR55##                                                                                         ##STR56##    2,3- dimethyl- maleic anhydride          14                                                                                ##STR57##          H.sub.2 NCH.sub.2COOH                                                                       2,3- dimethyl- maleic anhydride          15                                                                                ##STR58##          H.sub.2 N(CH.sub.2).sub.2 NHCH.sub.3                                                        2,3- dimethyl- maleic anhydride          16                                                                                ##STR59##                                                                                         ##STR60##    2,3- dimethyl- maleic anhydride          __________________________________________________________________________                              Melt-                                                                         ing                                                                           point/                                                   Reac-                                                                              Tem-      re-   boil-     NMR                                            tion pera-     crystal-                                                                            ing  Yield                                                                              (CDCl.sub.3)                              Ex.  time ture      lised point                                                                              % of δ in                                No.  hours                                                                              °C.                                                                        Solvent                                                                             from  °C.                                                                         theory                                                                             ppm                                       __________________________________________________________________________    10   8    reflux                                                                            anhy- ethyl 83-  66   1.95                                                    drous acetate/                                                                            86                                                                acetic                                                                              petrol-                                                                 acid  eum                                                                           ether                                                     11   5    reflux                                                                            anhy- iso-  101- 70   2.0                                                     drous propyl                                                                              102                                                               acetic                                                                              ether                                                                   acid                                                            12   16   reflux                                                                            anhy- methanol                                                                            164- 40   1.9                                                     drous       165                                                               acetic                                                                        acid                                                            13   2    reflux                                                                            anhy- methanol                                                                            200  95   2.0.sup.(**)                                            drous                                                                         acetic                                                                        acid                                                            14   3    reflux                                                                            anhy- ethyl 162- 30   2.0                                                     drous acetate                                                                             164                                                               acetic                                                                        acid        78°                                          15   1    reflux                                                                            benzene                                                                             --    0.1 mm                                                                             54   2.0                                                                 Hg;                                                                           melt-                                                                         ing                                                                           point                                                                         21-23°                                       16   1    25  ethyl water 83-  60   2.0                                                     acetate     85                                                  __________________________________________________________________________     .sup.(*) methyl protons of the dimethylmaleimidyl radical                     .sup.(**) DMSO-d.sub.6                                                   

EXAMPLE 17 ##STR61##

183.0 g (1.0 mol) of N-(3-hydroxypropyl)-dimethylmaleimide (obtained byreacting dimethylmaleic anhydride with 1,3-aminopropanol) and 111.3 g(1.1 mols) of triethylamine (dried over NaOH) are dissolved in 400 ml ofdiethyl ether (dried over Na) in a 750 ml sulphonation flask, which isfitted with a dropping funnel, with a pressure equalising device, acondenser and a thermometer, and the solution is cooled to 0° C. 104.5 g(1.0 mol) of methacrylic acid chloride are added dropwise to thissolution at such a rate that the temperature does not exceed 10° C.

When the reaction has ended, the reaction mixture is stirred until ithas warmed to room temperature (20°-25° C.)

The triethylamine hydrochloride which has precipitated during thereaction is now separated from the remaining reaction solution byfiltration. The ether extract is washed with slightly acidified wateruntil neutral, dried over Na sulphate and then concentrated in vacuowithout heating.

224.1 g (89.3% of theory) of the above imidyl derivative are obtained;n₂₀ ^(d) =1.4962.

Analysis for C₁₃ H₁₇ O₄ N (molecular weight 251): calculated C 62.1% H6.8% N 5.6% found C 62.3% H 7.0% N 5.4% NMR spectrum (CDCl₃): δ=1.95 ppm(methyl protons of the dimethylmaleimidyl radical).

EXAMPLE 18 ##STR62##

If, in Example 17, the equivalent amount of acrylic acid chloride isused in place of 104.5 g (1.0 mol) of methacrylic acid chloride and theprocedure is otherwise identical, 214.7 g (90.4% of theory) of the aboveimidyl derivative are obtained; n₂₀ ^(d) =1.4966.

Analysis for C₁₂ H₁₅ O₄ N (molecular weight 237): calculated C 59.2% H5.9% N 6.3% found C 58.8% H 5.9% N 6.0% NMR spectrum (CDCl₃): δ=1.95 ppm(methyl protons of the dimethylmaleimidyl radical).

Table III which follows indicates further compounds of the formula I,which were obtained according to the procedure described in Example 17by reacting N-(2-hydroxyethyl)-dimethylmaleimide (Examples 19 and 20),N-(2-hydroxypropyl)-dimethylmaleimide (Examples 21),N-(6-hydroxy-n-hexyl)-dimethylmaleimide (Example 22),N-(4-hydroxycyclohexyl)-dimethylmaleimide (Examples 23 and 24) andN-(6-hydroxy-n-hexyl)-tetrahyrophthalimide (Example 25) with methacrylicacid chloride or acrylic acid chloride.

                                      Table III                                   __________________________________________________________________________    Examples 19-25                                                                                               Yield                                                                             Analysis          NMR                      Example                                                                            Compound of               % of                                                                              calculated                                                                             found    (CDCl.sub.3) =           No.  the formula I             theory                                                                            C% H% N% C% H% N% ppm.sup.x                                                                           N.sub.20.sup.d     __________________________________________________________________________    19                                                                                  ##STR63##                91.4                                                                              60.8                                                                             6.4                                                                              5.9                                                                              60.6                                                                             6.6                                                                              5.3                                                                              1.95  1.4965             20                                                                                  ##STR64##                89.9                                                                              59.2                                                                             5.9                                                                              6.3                                                                              58.8                                                                             5.9                                                                              6.0                                                                              1.95  1.4966             21                                                                                  ##STR65##                92.1                                                                              62.1                                                                             6.8                                                                              5.6                                                                              62.6                                                                             6.9                                                                              4.5                                                                              1.95  1.4961             22                                                                                  ##STR66##                90.2                                                                              65.5                                                                             7.9                                                                              4.8                                                                              65.3                                                                             8.0                                                                              4.6                                                                              1.95  1.4962             23                                                                                  ##STR67##                82.3                                                                              65.9                                                                             7.2                                                                              4.8                                                                              65.4                                                                             6.9                                                                              4.6                                                                              1.96                     24                                                                                  ##STR68##                91.5                                                                              65.0                                                                             6.9                                                                              5.0                                                                              65.9                                                                             6.4                                                                              4.8                                                                              1.95                     25                                                                                  ##STR69##                89.0                                                                              67.7                                                                             7.9                                                                              4.4                                                                              66.8                                                                             7.8                                                                              4.3      1.5029             __________________________________________________________________________     .sup.x methyl protons of the dimethylmaleimidyl radical                  

EXAMPLES 26 ##STR70##

71.0 g (1.0 mol) of acrylic acid amide and 101.25 g of triethylamine,dissolved in 200 ml of anhydrous acetone, are initially introduced intoa 1,500 ml sulphonation flask which is fitted with a dropping funnel,with a pressure equalising device, a condenser and a thermometer. 257.5g (1.0 mol) of N-(caproic acid chloride)-dimethylmaleimide, dissolved in400 ml of anhydrous acetone, are added dropwise to this solution, whilstcooling with ice/water, at such a rate that the temperature does notexceed 40° C. When the reaction has taken place, the mixture is stirredfor 1 hour. The resulting triethylamine hydrochloride is then separatedfrom the remaining reaction solution by filtration. The acetone extractis concentrated in vacuo without heating.

For further working up, the residue is taken up in 1,000 ml of diethylether and washed with 4 times 1,000 ml of water. After drying with Nasulphate, the ether phase is concentrated in vacuo without heating.208.0 g (71.2% of theory) of the above imidyl derivative are obtained;melting point about 20° C.

Analysis for C₁₅ H₂₀ O₄ N₂ (molecular weight 292): calculated C 61.6% H6.8% O 21.9% N 9.6 found C 60.9 H 6.4 O 21.7 9.5 NMR spectrum (CDCl₃):δ=1.94 ppm (methyl protons of the diemthylmaleimidyl radical).

The acid chloride used in the above example is obtained in a mannerwhich is in itself known by reacting the N-(caproicacid)-2,3-dimethylmaleimide described in Example 9 with thionylchloride.

EXAMPLE 27 ##STR71##

140.0 g (1.0 mol) of N-amino-dimethylmaleimide and 111.3 g (1.1 mols) oftriethylamine (dried over NaOH) are dissolved in 2,500 ml ofdichloromethane in a 4,500 ml sulphonation flask, which is fitted with adropping funnel, with a pressure equalising device, a condenser and athermometer, and the solution is cooled to 0° C.

104.5 g (1.0 mol) of methacrylic acid chloride are added dropwise tothis solution at such a rate that the temperature does not exceed 10° C.

When the reaction has taken place, the mixture is heated to 40° C. andthen stirred at this temperature for one hour.

After cooling to about 20°-25° C., the reaction solution is washed withwater until neutral. The dichloromethane extract is dried over Mgsulphate and then concentrated to dryness in vacuo without heating.187.6 g (90.2% of theory) of the aboveN-[1-aza-3-methyl-2-oxobut-3-enyl]-2,3-dimethylmaleimide are obtained;melting point 105° C. Analysis for C₁₀ H₁₂ O₃ N (molecular weight 208):calculated C 57.69% H 5.81% N 13.46% found C 57.46% H 5.69% N 12.98% NMRspectrum (CDCl₃): δ=1.96 ppm (methyl protons of the dimethylmaleimidylradical).

EXAMPLE 28 ##STR72##

102.05 g (0.4 mol) of 5-nitrotrimellitic acid are suspended in 260 ml ofwater and 48 g (1.2 mols) of sodium hydroxide dissolved in 240 ml ofwater are added. The resulting solution is hydrogenated at 42° C. in thepresence of 10 g of a palladium-on-charcoal catalyst containing 5% byweight of Pd. The reaction solution is filtered and the filtrate isconcentrated to a volume of about 150 ml and first 75 ml of toluene andthen 50.44 g (0.4 mol) of dimethylmaleic anhydride are added and themixture is boiled under reflux for 10 minutes. The reaction mixture isevaporated to dryness, the residue is dissolved in 500 ml of hot waterand the solution is acidified with 438 ml of 10% strength hydrochloricacid and cooled to 0°-5° C. and 14 ml of 32% strength hydrochloric acidare added. The precipitate which has separated out is filtered off,rinsed with 50 ml of ice water and dried at 80° C. in a drying cabinet.The yield of 5-dimethylmaleimidyl-trimellitic acid is 111.1 g (83% oftheory).

EXAMPLE 29 ##STR73##

140 ml of acetic anhydride are added to 76.64 g (0.23 mol) of thedimethylmaleimidyl-trimellitic acid prepared according to Example 28 andthe mixture is heated to the boil. The acid dissolves completely withina short time. The solution is evaporated to dryness, the residue isboiled with 180 ml of benzene and the precipitate is filtered off anddried at 80° C. in a drying cabinet. 51.8 g (71%) of5-dimethylmaleimidyl-trimellitic anhydride are obtained; melting point181°-185°.

EXAMPLE 30 ##STR74##

50.43 g (0.16 mol) of the 5-dimethylmaleimidyl-trimellitic anhydrideprepared according to Example 29 are suspended in 320 ml of benzene,17.5 ml (0.24 mol) of thionyl chloride and 0.5 ml ofN,N-dimethylformamide are added and the mixture is heated to 90° C.,whilst stirring. The turbid solution which has formed after boiling for15 minutes is filtered and the filtrate is cooled.5-Dimethylmaleimidyl-trimellitic anhydride-chloride, which hascrystallised out over sodium acetate, is dried at 80° C./0.5 mm Hg.Yield: 29.6 g (55%); melting point 184°-185° C.

Analysis for C₁₅ H₈ NO₆ Cl (molecular weight 333.68): calculated C53.99%; H 2.42%; N 4.20%; Cl 10.63% found C 53.69%; H 2.39%; N 3.95%; Cl10.92%.

EXAMPLE 31 ##STR75##

3.33 g (0.01 mol) of the 5-dimethylmaleimidyl-trimelliticanhydride-chloride prepared according to Example 30 are dissolved indioxane. 0.58 ml (0.01 mol) of ethanol are then added dropwise and thereaction mixture is stirred overnight. The reaction mixture is thenheated to 85° C. for 15 minutes and cooled and 35 ml of cyclohexane areadded slowly. The product which has crystallised out is filtered off,rinsed with 5 ml of cyclohexane and dried at 100° C. in a dryingcabinet. 2.49 g (72.5% of theory) of 5-dimethylmaleimidyl-trimelliticanhydride-ethyl ester are obtained; melting point 172°-174° C.

Analysis for C₁₇ H₁₃ NO₇ (molecular weight 343.29): calculated C 59.48%;H 3.82%; N 4.08% found C 59.17%; H 3.80%; N 4.25%.

EXAMPLE 32 ##STR76##

23.35 g (0.07 mol) of the 5-dimethylmaleimidyl-trimelliticanhydride-chloride prepared according to Example 30 are dissolved in 70ml of dioxane, 13.04 g (0.07 mol) of lauryl alcohol, dissolved in 25 mlof dioxane, are added whilst stirring and the mixture is left to standovernight. The solution is then evaporated.

35 ml of diethyl ether are added to the residue. After stirring for 3hours, 35 ml of cyclohexane are added to the resulting fine crystallinesuspension and the precipitate is filtered off and dried at 50° C. in adrying cabinet. 24 g (71% of theory) of 5-dimethylmaleimidyl-trimelliticanyhydride-lauryl ester are obtained; melting point 93° C.

Analysis for C₂₇ H₃₃ NO₇ (molecular weight 483.56): calculated: C67.06%; H 6.88%; N 2.90% found: C 66.82%; H 6.97%; N 2.98%.

EXAMPLE 33 ##STR77##

76.5 g (0.34 mol) of disodium 5-amino-isophthalate are dissolved in 200ml of water at 40°-50° C. in a 1 liter three-necked flask, which isprovided with a reflux condenser and a stirrer. 44.2 g (0.35 mol) ofdimethylmaleic anhydride, dissolved in 300 ml of dimethylacetamide, areadded to this solution, whilst stirring. The slightly yellowish solutionis then boiled to 100° C. for 30 minutes, whilst stirring continously.The solution is then acidified (Congo Blue), at a temperature of95°-100° C., with 10% strength hydrochloric acid. After the mixture hascooled to room temperature, the resulting precipitate is filtered off.The crude product is dried at 90° C. in vacuo. 68.5 g (70% of theory) of5-dimethylmaleimidyl-isophthalic acid are obtained; melting point above250° C.

Analysis for C₁₄ H₁₁ NO₆ (molecular weight 289): calculated: C 59.1%; H3.8%; N 4.8% found: C 58.2%; H 4.0%; N 4.9%.

EXAMPLE 34 ##STR78##

50.9 g (0.176 mol) of 5-dimethylmaleimidyl-isophthalic acid and 500 mlof thionyl chloride are boiled together under reflux, in a 1 litersingle-necked flask, which is provided with a reflux condenser, until aclear solution has formed. About 5 drops of pyridine are added in orderto catalyse the reaction. The reaction mixture is then evaporated todryness in a rotary evaporator, an orange-red residue being obtained.

The orange-red residue is then extracted, in a hot extractor, withanhydrous cyclohexane, the acid chloride being obtained. After coolingto 20°-25° C., the acid chloride which has precipitated is separated offby filtration and recrystallised from cyclohexane (20 g of acidchloride/500 ml of cyclohexane).

Yield: 39.3 g (80.2% of theory); melting point 115.5°-116.5° C.

Analysis for C₁₄ H₉ Cl₂ NO₄ (molecular weight 326.138): calculated: C51.56%; H 2.78%; N 4.29%; Cl 21.74% found: C 51.5%; H 2.9%; N 4.4%; Cl21.6%.

EXAMPLE 35 ##STR79##

47.2 g (0.145 mol) of 5-dimethylmaleimidyl-isophthalic acid dichlorideare dissolved in 94.4 g of dry acetone.

This solution is boiled under reflux; whilst boiling, 1 liter of drymethanol is gradually added dropwise. A white product precipitates out.When the addition is complete, the reaction mixture is cooled to about20°-25° C. and the residue is filered off. After drying, 45.6 g (99% oftheory) of pale yellowish crystals of the above diester are obtained;melting point 229°-234° C. (recrystallised from diethyl ketone andsublimed).

H¹ NMR: (DMSO-d₆, TMS=0) 6H at 1.96 ppm (methyl protons).

Analysis for C₁₆ H₁₅ NO₆ (molecular weight 317): calculated: C 60.56%; H4.75%; N 4.41% found: C 61.0%; H 4.8%; N 4.7%.

EXAMPLE 36 ##STR80##

7.20 g (0.039 mol) of disodium 3,5-diaminophthalate, dissolved in 200 mlof water, are added to a solution of 8.82 g (0.078 mol) ofdimethylmaleic anhyride in 80 ml of toluene. This mixture is boiledunder reflux for 1 hour. It is then evaporated to dryness in a rotaryevaporator, the residue is dissolved, at 90° C., in 100 ml ofN,N-dimethylacetamide and 50 ml of water and the solution is renderedacid to Congo Blue with 10% strength hydrochloric acid. After cooling,the slurry-like mixture is filtered and the residue is rinsed withacetone and then dried in vacuo at 80° C. The dry residue is thensuspended in 100 ml of acetic anhydride and this mixture is warmed toabout 100° C. for 1 hour. It is then evaporated to dryness and theresidue is recrytallised from 1,2-dichlorobenzene. 8.9 g (69% theory) of3,5-bis-(dimethylmaleimidyl)-phthalic anhydride are obtained: colour:light brownish; melting point 298° C. (decomposition). H¹ NMR: (DMSO-d₆,TMS= 0) 2H (aromatic) 7.94 and 7.98 ppm, 12H (methyl protons 1.98 ppm).

Analysis for C₂₀ H₁₄ N₂ O₇ (molecular weight 394.12): calculated:C60.92%; H 3.58%; N 7.11% found: C 60.67%; H 4.44%; N 7.32%.

EXAMPLE 37 ##STR81##

27.1 g (0.1 mol) of 3-dimethylmaleimidyl-phthalic anhydride and 13 g(0.1 mol) of freshly distilled 2-hydroxyethyl methacrylate are dissolvedin 500 ml of tetrahydrofurane. About 0.5 ml of triethylamine and 0.05 gof hydroquinone are added to this solution. The reacton mixture is nowstirred for 24 hours at 50° C. and under dry nitrogen. When the reactionhas ended, the solvent is evaporated off by means of a rotaryevaporator. The resulting oil is taken up in 500 ml of diethyl ether andthe ether soltion is washed, first with 100 ml of 0.5 N sodium hydroxidesolution and then with twice 200 ml of water. The ether solution is thenevaporated, the above imidyl derivative(N-[2,3-dicarboxyphenyl-3-(5-methyl-3-oxa-hex-5-enyl)ester]-dimethylmaleimide) being obtained in 98% yield; n₄₀ ^(d) =1.5155.

Analysis for C₂₀ H₁₉ NO₈ (molecular weight 401): calculated: C 59.85%; H4.72%; N 3.49% found: C 60.3%; H 5.8%; N 3.5% NMR spectrum (CDCl₃);δ=1.98 ppm (methyl protons).

EXAMPLE 38 ##STR82##

48.3 g (0.1 mol) of the 5-dimethylmaleimidyl-trimelliticanhydride-lauryl ester prepared according to Example 32 and 13 g (0.1mol) of freshly distilled methacrylic acid 2-hydroxyethyl ester aredissolved in 500 ml of tetrahydrofurane. About 0.5 ml of triethylamineand 0.05 g of hydroquinone are added to this solution. The mixture isnow stirred for 24 hours at 50° C. and under dry nitrogen. When thereaction has ended, the solvent is evaporated off by means of a rotaryevaporator. The resulting oil is taken up in 500 ml of ether and theether solution is washed first with 100 ml of 0.5 N sodium hydroxidesolution and then with twice 200 ml of water. The ether solution is thenevaporated, 60 g (98% of theory) of the above imidly derivative(=N-(2,3,5-tricarboxyphenyl-3-{-5-methyl-3-oxa-4-oxa-hex-6-enyl}-5-[dodecyl]diester)-dimethylmaleimide) being obtained in the form of a paleyellowish, highly viscous oil; n₂₀ ^(d) =1.5046.

Analysis for C₂₇ H₃₃ O₇ N (molecular weight 483): calculated: C 64.59%;H 7.06%; N 2.28% found: C 64.33%; H 7.61%; N 2.45% NMR spectrum (CDCl₃):δ=1.98 ppm (methyl protons).

EXAMPLE 39

The 3,5-(bis-dimethylmaleimidyl)-phthalic anhydride obtained accordingto Example 36 is reacted with freshly distilled methacrylic acid2-hydroxyethyl ester, in a manner analogous to that described in Example38. 98% of theory of the compound of the formula ##STR83## are obtained;melting point 42° C.

Analysis for C₂₆ H₂₄ O₁₀ N₂ (molecular weight 542): calculated: C 59.5%;H 4.7%; N 5.3% found: C 59.3%; H 4.9%; N 5.1% NMR spectrum (CDCl₃):δ=1.98 ppm (methyl protons).

EXAMPLE 40 ##STR84##

49 g (0.5 mol) of maleic anhydride, dissolved in 400 ml of diethylether, are added, in the course of about 10 minutes, whilst stirring, to70 g (0.5 mol) of N-amino-dimethylmaleimide, dissolved in 200 ml ofmethylene chloride, the mixture is stirred overnight at about 20°-25° C.and the resulting precipitate is filtered off and dried (in vacuo at 60°C. for 2 hours). 107 g (90% of theory) of white amide-acid are obtained;melting point 167°-168° C.

Analysis for C₁₀ H₁₀ N₂ O₅ (molecular weight 238.20): calculated: C50.43%; H 4.23%; N 11.76% found: C 50.59%; H 4.30%; N 11.90%.

9.6 g (0.040 mol) of this amide-acid are stirred with 40 ml of aceticanhydride at 80° C. until everything has gone into solution (about 20minutes). The solution is concentrated well, at 60° C./15 mm Hg, in arotary evaporator. 9.6 g of a crude product remain and can be purifiedby recrystallisation from methanol or by sublimation at 110° C./0.1 mmHg. After purification, 7.9 g (90% of theory) of whiteN-dimethylmaleimido-maleimide are obtained; melting point 116°-120° C.

Analysis for C₁₀ H₈ N₂ O₄ (molecular weight 220.18): calculated: C54.55%; H 3.66%; N 12.73% found: C 54.55%; H 3.68%; N 13.07%.

EXAMPLE 41 ##STR85##

70.0 g (0.31 mol) of the N-(4-hydroxyphenyl)-dimethylmaleimide obtainedaccording to Example 13 are dissolved in 500 ml of acetone. 41.0 ml(0.58 mol) of ally bromide and 44.2 g of potassium carbonate are thenadded; the reaction mixture is warmed to 55°-58° C. and kept at thistemperature for 4 hours, whilst stirring. The reaction mixture is thenpoured into 500 ml of ice/water. TheN-(allyloxyphenyl)-dimethylmaleimide precipitates out in the form of apale yellow crystals. It is filtered off and dried in vacuo at 70° C.;melting point 122°-123° C.; yield 80.7 g =98% of theory.

EXAMPLE 42 ##STR86##

14.7 g (0.1 mol) of the sodium salt of dimethylmaleimide are introducedinto 50 ml (0.5 mol) of 2-chloroethyl vinyl ether. After adding 0.5 g ofmethyltriethylammonium iodide, the mixture is warmed to 100°-105° C. andstirred at this temperature for 4 hours. The sodium chloride which hasprecipitated out is filtered off and the excess 2-chloroethyl vinylether is distilled off in vacuo. 18 g of a dark brown oil remain andthis solidifies on cooling. For purification, the product isrecrystallised from heptane; melting point 75° C.

EXAMPLE 43 ##STR87##

0.5 ml of a 1% strength solution of hexachloroplatinic acid in ethyleneglycol dimethyl ether is added to a solution of 35 g (0.136 mol) ofN-(4-allyloxyphenyl)-dimethylmaleimide (prepared according to Example41) in 500 ml of toluene and a solution of 20 g (0.174 mol) ofdichloromethylsilane in 100 ml of toluene is added dropwise to theresulting mixture at 105° C. and with the exclusion of moisture. Thereaction mixture is stirred at 105°-110° C. for 3 hours and the solventis then distilled off. Melting point 122°-123°.

Analysis: calculated: C 51.6%; H 5.2%; N 3.8%; Cl 19.0%; Si 7.6%. found:C 51.8%; H 5.3%; N 3.8%; Cl 18.6%; Si 7.7%.

EXAMPLE 44 ##STR88##

If, in place of 20 g of dichlormethylsilane, the equivalent amount ofdipropoxymethylsilane is used and in other respects the procedure is asindicated in Example 43,dipropoxy-methyl-3-(4'-dimethylmaleimidyl-phenoxy)-propylsilane isobtained. For purification, the product is distilled under 0.001 mm Hgand at 198°-203° C.; melting point 87° C.

Analysis: calculated: C 63.0%; H 7.9%; N 3.3%; Si 6.7%. found: C 62.9%;H 8.0%; N 3.5%; Si 6.9%.

EXAMPLE 45 ##STR89##

In accordance with the procedure described in Example 1, 12.61 g (0.1mol) of dimethylmaleic anhydride are reacted,in the melt, with 31.15 g(0.1 mol) of the above aminosilane. The resulting oily, pale yellowishcoloured product is distilled off.

Yield: 32.3 g (77% of theory); Boiling point/10⁻³ mm Hg; 192°-200° C.Analysis for C₂₂ H₃₃ N₁ O₅ Si₁ (molecular weight 419.59): calculated: C62.9%; H 7.9%; N 3.3%; Si 6.6%. found: C 62.7%; H 8.1%; N 3.4%; Si 6.9%.

The dipropoxy-methyl-3-(4'-dimethylmaleimidylphenoxy)-propylsilaneobtained according to the above example can be converted into thecorrespondingdichloro-methyl-3-(4'-dimethylmaleimidyl-phenoxy)-propylsilane of theformula ##STR90## by reaction with suitable chlorinating agents, such asthionyl chloride or polyacrylic acid chloride.

The aminosilane used in the above example is obtained in a manner whichis in itself known by an addition reaction of methyl-di-n-propoxysilanewith 4-allyloxyaniline at about 100° C. in the presence of H₂ PtCl₆ asthe catalyt.

EXAMPLE 46 ##STR91##

In accordance with the procedure described in Example 1, 12.61 g (0.1mol) of dimethylmaleic anhydride are reacted in the melt with 32.55 g(0.1 mol) of the above aminosilane. The resulting oily, pale yellowishproduct is distilled off.

Yield: 38.6 g (80% of theory); Boiling point/10⁻³ mm Hg: 200°-205° C.Analysis for C₂₃ H₃₅ N₁ O₅ Si (molecular weight 433.62): calculated: C63.71%; H 8.14%; N 3.23%; Si 6.48%. found: C 63.5%; H 8.3%; N 3.5%; Si6.5%.

The compound of the formula ##STR92## is obtained by reacting theproduct with thionyl chloride or polymethacrylic acid chloride.

The aminosilane used in the above example is obtained in a manner whichis in itself known by an addition reaction of methyl-di-n-propoxysilanewith 4-methylallyloxysilane at about 100° C. in the presence of H₂ PtCl₆as the catalyst.

The dimethylmaleimidyl derivatives described above can also be obtainedin comparable yields by an addition reaction ofmethyl-di-n-propoxysilane or methyldichlorosilane with thedimethylmaleimidyl derivative of the formula ##STR93## The additionreaction is carried out, for example, in boiling toluene and using H₂PtCl₆ as the catalyst.

In the above Examples 45 and 46 it is also possible to employ equivalentamounts of the corresponding 3-aminosilanes or mixtures of 3-and4-aminosilanes or mixtures of 3-and 4-aminosilanes in place of the4-amino-silanes described.

EXAMPLE 47 ##STR94##

In accordance with the procedure described in Example 1, 12.61 g (0.1mol) of dimethylmaleic anhydride are reacted in the melt with 32.55 g(0.1 mol) of the above aminosilane. The oily, pale yellow colouredproduct is distilled off. Yield 32.6 g (75% of theory); boilingpoint/10⁻³ mm Hg: 200°-205° C.

Analysis for C₂₃ H₃₅ N₁ O₅ Si (molecular weight 433.62):

calculated :C 63.71%; H 8.14%; N 3.23%; Si 6.46%.

found: C 63.1%; H 7.9% N 3.5%; Si 6.7%.

The above dimethylmaleimidyl derivative can also be manufactured by anaddition reaction of methyl-di-n-propoxy-silane with thedimethylmaleimidyl compound of the formula ##STR95## in boiling tolueneand using H₂ PtCl₆ as the catalyst.

EXAMPLE 48 ##STR96##

12.61 g (0.1 mol) of dimethylmaleic anhydride are reacted, in the mannerdescribed in the preceding Examples 45 -47, with 42.85 g (0.1 mol) ofthe above aminosilane. The resulting solid, yellow coloured reactionproduct is recrystallised from a 1:1 mixture by volume of dibutylether/hexane; melting point 106°-108° C.

Analysis for C₃₀ H₃₆ N₂ 0₇ Si₁ (molecular weight 564.71):

calculated: C 63.8% ; H 6.4% ; N 5.0% ; Si 5.0%.

found: C 63.4% ; H 6.4% ; N 5.2% ; Si 5.1%.

The compound of the formula ##STR97## is obtained by reacting theproduct with thionyl chloride or polyacrylic acid chloride.

The above dimethylmaleimidyl derivatives can also be obtained by anaddition reaction of methyl-di-n-propoxysilane or methyl-dichlorosilanewith the compound of the formula ##STR98##

EXAMPLE 49 ##STR99##

12.61 g (0.1 mol) of dimethylmaleic anhydride and 50.06 g (0.1 mol) ofthe above aminosilane reacted in a manner analogous to that described inthe preceding Examples 45-47. The resulting solid, yellow colouredreaction product is recrystallised from a 1:3 mixture by volume ofdibutyl ether/hexane; melting point 110° C.

EXAMPLE 50

137.4 g (0.34 mol) of the dimethylmaleimidyl derivative obtainedaccording to Example 37, together with 0.8 g of azo-isobutyronitrile,are dissolved in 625 ml of tetrahydrofurane. This mixture is polymerisedfor 5 hours under gentle reflux (about 80° C.), whilst stirring andcontinuously under a nitrogen atmosphere. When the reaction has ended,the reaction mixture is cooled to 20°-25° C. and the polymer isprecipitated by adding the reaction solution dropwise to 5 liters ofhexane. 120.7 g (88% of theory) of the polymer, which consists ofstructural elements of the formula ##STR100## are obtained.

NMR (chlorobenzene, TMS-O): δ=1.96 ppm (methyl protons of thedimethylmaleimidyl radical); inherent viscosity 0.12 dl/g (0.5% strengthsolution in N,N-dimethyl-formamide, at 20° C.).

EXAMPLE 51

14.4 g (0.02 mol) of the dimethylmaleimidyl derivative obtainedaccording to Example 38, together with 20 g (0.2 mol) of methacrylicacid methyl ester, 10 g (0.07 mol) of methacrylic acid 2-hydroxyethylester and 0.4 g of azo-isobutyro-nitrile, are dissolved in 270 ml oftetrahydrofurane. This mixture is polymerised under gentle reflux (about80° C.), whilst stirring and continuously under a nitrogen atmosphere.When the reaction has ended (reaction time about 7 hours), the mixtureis cooled to 20°-25° C. and the polymer is precipitated by adding thereaction solution dropwise to 2 liters of hexane. 27 g (60% of theory)of the polymer, which consists of structural elements of the formula##STR101## (a =32% by weight; b =46% by weight and c =22% by weight) areobtained.

NMR (chlorobenzene, TMS-O): δ=1.94 ppm (methyl) protons of thedimethylmaleimidyl radical); inherent viscosity 0.19 dl/g (0.5% strengthsolution in N,N-dimethylformamide at 20° C.).

EXAMPLE 52

Copolyamide of ##STR102##

(a) Preparation of the acid chloride mixture (90:10 mol %)

40.20 g of isophthalic acid dichloride and 7.17 g of5-dimethylmaleimidyl-isophthalic acid dichloride, prepared according toExamples 33/34, are melted together at 70° C., the melt is allowed tosolidify and the solid is crumbled.

(b) Polycondensation

21.47 g of m-phenylenediamine are dissolved in 190 ml ofN,N-dimetylacetamide, the solution is cooled to -25° C. using a bath ofsolid carbon dioxide and, whilst stirring vigorously and under an inertgas atmosphere, 43.07 g of the acid chloride mixture obtained accordingto (a) are added in the solid form. During the addition, the temperaturerises to about +30° C. The cooling bath is removed and the reactionproduct is stirred for a further 3 hours at 20°-25° C. After dilutingwith 190 ml of N,N-dimethylacetamide, the polymer is precipitated, in amixer, by means of water, washed with water until neutral and driedovernight at 120° C. in a vacuum drying cabinet. A fibrous, almost whitepolymer which has an inherent viscosity of 0.7 dl/g (0.5% strengthsolution in N,N-dimethylacetamide, measured at 25° C.), is soluble inN,N-dimethylformamide and N,N-dimethylacetamide without the addition ofa salt and can be processed to films in a manner which is in itselfknown, is obtained in quantitative yield. The films can be crosslinkedby irradiation with UV light, insoluble films being formed.

EXAMPLE 53

38.446 g (0.192 mol) of 4,4'-diaminodiphenyl ether are dissolved in 200ml of anhydrous N,N-dimethylacetamide, under nitrogen. The solution iscooled to -15° C. A mixture of 15.00 g (0.048 mol) of5-dimethylmaleimidyl-trimellitic anhydride-chloride and 30.322 g (0.144mol) of trimellitic anhydride-chloride are sprinkled in at -15° C. to-5° C., whilst stirring vigorously. A slightly exothermic reaction takesplace and a viscous solution is formed, which is diluted with 100 ml ofN,N-dimethlacetamide and gradually warmed to 20°-25° C. After stirringfor 2 hours at 20°-25° C., a further 100 ml of N,N-dimethylacetamide areadded. The hydrochloric acid formed during the reaction is precipitatedwith 19.42 g (0.192 mol) of triethylamine. The salt which hasprecipitated out is filtered off. The resulting clear solution has aninherent viscosity of 0.65 dl/g (0.5% strength solution inN,N-dimethylacetamide at 25° C.).

The resulting polymer solution is suitable, if appropriate after theaddition of a sensitiser, such as thioxanthone, for the manufacture ofphotochemically crosslinkable films and sheets, for example forphotographic purposes. Films and sheets of this type can be obtainedaccording to known methods, for example by casting, evaporating thesolvent and cyclising the amide-acid to the amide-imide at elevatedtemperature in vacuo, and crosslinked by means of UV light to giveproducts which are resistant to solvents.

The cyclised polymer which has not been crosslinked is soluble inN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-pyrrolidone andconcentrated sulphuric acid.

EXAMPLE 54

Copolyamide of: ##STR103##

19.69 g (0.0993 mol) of 4,4'-diaminodiphenylmethane are dissolved in 150ml of anhydrous N,N-dimethylacetamide and the solution is cooled to -20°C. under a nitrogen atmosphere. 16.74 g (0.07 mol) of sebacic aciddichloride are added dropwise at a temperature of -10° C. to -20° C. and9.78 g (0.03 mol) of 5-dimethylmaleimidyl-isophthalic acid dichlorideare then added all at once. The cooling bath is removed and the reactionmixture is stirred for a further 3 hours at 20°-25° C. The resultinghighly viscous, yellowish reaction product is precipitated, in a mixer,by means of water, washed with water until neutral and dried at 80° C.in vacuo for 24 hours. A yellowish, fibrous polymer, which has aninherent viscosity of 0.81 dl/g (0.5% strength solution in concentratedsulphuric acid, at 25° C.), is obtained in quantiative yield. Thepolymer is soluble in N,N-dimethylacetamide which contains 5% by weightof LiCl and is suitable for the manufacture of transparent films whichcan be crosslinked by light.

EXAMPLE 55

100 g of "Gantrez 119", which is a maleic anhydride copolymer consistingof structural elements of the formula ##STR104## (anhydride content 0.64mol %), and 82 g (0.66 mol) of theN-(4-hydroxycyclohexyl)-dimethylmaleimide prepared according to Example1 are dissolved in 400 ml of dry tetrahydrofurane. 1 ml of concentratedsulphuric acid is then added. The reaction mixture is kept at 80° C. for72 hours, whilst stirring. The resulting homogeneous solution is thenpoured into 1 liter of hexane. The precipitate which is deposited isseparated off, washed several times with diethyl ether, dried at 40° C.in vacuo and ground to a powder.

EXAMPLE 56

Anodised aluminium plates are coated, by the whirler-coating process(2,000-3,000 revolutions)minute), with a10% strength solution, incyclohexanone, of the polymerobtained according to Example 55, whichsolution also contains 0.5% by weight of thioxanthone (sensitiser). Thecoated plates are dried at a temperature of about 30° C.

The plates treated in this way are exposed under a photographic stepwedge (12 steps) for 10 seconds by the contact process using a 400 Wattmercury high-pressure lamp at a distance of 40 cm. The plates are thenwashed (fixed) with a 5% strength aqueous solution of NaHCO₃ and dyedwith a 1% strength aqueous solution of the dyestuff of the formula##STR105## The plates are then washed with water for 2-3 seconds anddried. All of the parts with screen dots have been recorded. 10 wedgesteps are clearly visible. Fixing, dyeing and washing can be carried outin a conventional roll processor.

EXAMPLE 57 ##STR106##

28 g (0.224mol) of dimethylmaleimide are suspended in 600 ml of toluene,in a flask which is provided with a stirrer and a water separator, andthe suspension is heated to the boil. 12.5 g (0.224 mol) of finelypowdered potassiium hydroxide are introduced in portions into thereaction mixture and the reaction mixture is boiled under reflux for afurther 2 hours, the theoretical amount of water (about 4.5 ml) beingseparated off. The reaction mixture is then cooled and filtered and theresidue (potassium salt of dimethylmaleimide) is washed with acetone anddried.

30 g (0.184 mol) of the above potassium salt of dimethylmaleimide and0.05 g of tetramethylammonium chloride are suspended in 175 g (1.89 mol)of epichlorohydrin. The suspension is boiled under reflux for 18 hours,whilst stirring, and then filtered. The excess epichlorohydrin isremoved from the filtrate by distillation under reduced pressure. 30 gof a viscous, pale brown liquid, which has an epoxide content of 4.9equivalents/kg (calculated 5.5 equivalents/kg), are obtained. The NMRspectrum of the product obtained is compatible with that ofN-glycidyl-dimethyl-maleimide.

In the above example it is also possible to use the corresponding sodiumsalt in place of the potassium salt of dimethylmaleimide. This sodiumsalt is prepared as follows: 25.0 g (0.2 mol) of dimethylmaleimide aredissolved in 20 ml of methanol. 10.8 g (0.2 mol) of sodium methylate,dissolved in 100 ml of methanol, are then added dropwise to the reactionmixture at 20°-25° C., whilst stirring. After two hours 100 ml ofacetone are added and the crystals which have precipitated are filteredoff and dried.

Yield: 23.5 g (80% of theory) of the Na salt of dimethylmaleimide.

Analysis for C₆ H₆ NO₂ Na (molecular weight 147.1):

calculated: Na 15.6%.

found: Na 15.5%.

The NMR spectrum of the substance obtained is compatible with that ofthe sodium salt of dimethylmaleimide.

I claim:
 1. A compound wherein n is 1 or 2, when n is l, X is ##STR107##or glycidyl, where R₅ and the two R₄ 's each denote OH, Cl or alkoxy of1 to 12 carbon atoms; and the two R₆ 's have the same meaning as R₄ orconjointly represent --0--; and when n is 2, Y is phenylene,1,4-cyclohexylene, naphthtlene, ##STR108##
 2. A compound according toclaim 1 wherein n is l and X denotes ##STR109## and R₄, R₅ and R₆ aredefined as in claim
 1. 3. A compound according to claim 1 wherein n is2, Y is p-phenylene and X is OH.
 4. A compound according, to claim 1wherein n is 2, Y is 1,4-cyclohexylene and X is OH.
 5. A compoundaccording to claim 1 wherein n is 2, Y is p-phenylene and X is COOH orNH₂.
 6. A compound according to claim 10 wherein n is 1 and X is##STR110##
 7. A compound according to claim 1 wherein n is 1 and X isglycidyl.